Soil sampling and analysis for volatile organic compounds

Concerns over data quality have raised many questions related to sampling soils for volatile organic compounds (VOCs). This paper was prepared in response to some of these questions and concerns expressed by Remedial Project Managers (RPMs) and On-Scene Coordinators (OSCs). The following questions are frequently asked:

1. Is there a specific device suggested for sampling soils for VOCs?
2. Are there significant losses of VOCs when transferring a soil sample from a sampling device (e.g., split spoon) into the sample container?
3. What is the best method for getting the sample from the split spoon (or other device) into the sample container?
4. Are there smaller devices such as subcore samplers available for collecting aliquots from the larger core and efficiently transferring the sample into the sample container?
5. Are certain containers better than others for shipping and storing soil samples for VOC analysis?
6. Are there any reliable preservation procedures for reducing VOC losses from soil samples and for extending holding times?

Guidance is provided for selecting the most effective sampling device for collecting samples from soil matrices. The techniques for sample collection, sample handling, containerizing, shipment, and storage described in this paper reduce VOC losses and generally provide more representative samples for volatile organic analyses (VOA) than techniques in current use. For a discussion on the proper use of sampling equipment the reader should refer to other sources (Acker, 1974; U.S. EPA, 1983; U.S. EPA, 1986a). Soil, as referred to in this report, encompasses the mass (surface and subsurface) of unconsolidated mantle of weathered rock and loose material lying above solid rock. Further, a distinction must be made as to what fraction of the unconsolidated material is soil and what fraction is not. The soil component here is defined as all mineral and naturally occurring organic material that is 2 mm or less in size. This is the size normally used to differentiate between soils (consisting of sands, silts, and clays) and gravels. Although numerous sampling situations may be encountered, this paper focuses on three broad categories of sites that might be sampled for VOCs:

1. Open test pit or trench.
2. Surface soils (<5 ft in depth).
3. Subsurface soils (>5 ft in depth).

     

Cumulative impact assessment in environmental planning: A coastal wetland watershed example

Several theoretical, analytical, and institutional difficulties have impeded the development and application of the assessment of cumulative environmental impacts. Watershed development on coastal wetlands offers an ideal context for evaluating the land disturbance target approach to cumulative impact assessment. A model land use planning system involving a time series approach was developed for Elkhorn Slough in California. The approach included four major components: evaluation of erosion susceptibility, measurement of land disturbance, establishment of a land disturbance target, and a comparison of existing and target land disturbance values. Further research is needed to test the transferability of the approach in a wide range of coastal watersheds and to verify the applicability of the methods to other cumulative impact problems.     

Analysing the sensitivity behaviour of two hydrology models

Recently, the New Morris Method has been presented as an effective sensitivity analysis tool for mathematical models. The New Morris Method estimates the sensitivity of an output parameter to a given set of input parameters (first-order effects) and the extent these parameters interact with each other (second-order effects). This method requires the specification of two parameters (runs and resolution) that control the sampling of the output parameter to determine its sensitivity to various inputs. The criteria for these parameters have been set on the analysis of a well-behaved analytical function (see Cropp and Braddock, Reliab. Eng. Syst. Saf. 78:77–83, 2002), which may not be applicable to other physical models that describe complex processes. This paper will investigate the appropriateness of the criteria from (Cropp and Braddock, 2002) and hence the effectiveness of the New Morris Method to determine the sensitivity behaviour of two hydrologic models: the Soil Erosion and Deposition System and Griffith University Representation of Urban Hydrology. In the first case, this paper will separately analyse the sensitivity of an output parameter on a set of input parameters (first- and second-order effects) for each model and discuss the physical meaning of these sensitivities. This will be followed by an investigation into the sampling criteria by exploring the convergence of the sensitivity behaviour for each model as the sampling of the parameter space is increased. By comparing these trends to the convergence behaviour from Cropp and Braddock (2002), we will determine how well the New Morris Method estimates the sensitivity for each model and whether the sampling criteria are appropriate for these models. It will be shown that the New Morris Method can provide additional insight into the functioning of these models, and that, under a different metric, the sensitivity behaviour of these models does converge confirming the sampling criteria set by Cropp and Braddock.     

The efficacy of protoporphyrin as a predictive biomarker for lead exposure in canvasback ducks: Effect of sample storage time

We used 363 blood samples collected from wild canvasback dueks (Aythya valisineria) at Catahoula Lake, Louisiana, U.S.A. to evaluate the effect of sample storage time on the efficacy of erythrocytic protoporphyrin as an indicator of lead exposure. The protoporphyrin concentration of each sample was determined by hematofluorometry within 5 min of blood collection and after refrigeration at 4 °C for 24 and 48 h. All samples were analyzed for lead by atomic absorption spectrophotometry. Based on a blood lead concentration of 0.2 ppm wet weight as positive evidence for lead exposure, the protoporphyrin technique resulted in overall error rates of 29%, 20%, and 19% and false negative error rates of 47%, 29% and 25% when hematofluorometric determinations were made on blood at 5 min, 24 h, and 48 h, respectively. False positive error rates were less than 10% for all three measurement times. The accuracy of the 24-h erythrocytic protoporphyrin classification of blood samples as positive or negative for lead exposure was significantly greater than the 5-min classification, but no improvement in accuracy was gained when samples were tested at 48 h. The false negative errors were probably due, at least in part, to the lag time between lead exposure and the increase of blood protoporphyrin concentrations. False negatives resulted in an underestimation of the true number of canvasbacks exposed to lead, indicating that hematofluorometry provides a conservative estimate of lead exposure.The U.S. Government's right to retain a non-exclusive, royalty-free licence in and to any copyright is acknowledgedDeceased     

Scenario Analysis for the San Pedro River, Analyzing Hydrological Consequences of a Future Environment

Studies of future management and policy options based on different assumptions provide a mechanism to examine possible outcomes and especially their likely benefits and consequences. The San Pedro River in Arizona and Sonora, Mexico is an area that has undergone rapid changes in land use and cover, and subsequently is facing keen environmental crises related to water resources. It is the location of a number of studies that have dealt with change analysis, watershed condition, and most recently, alternative futures analysis. The previous work has dealt primarily with resources of habitat, visual quality, and groundwater related to urban development patterns and preferences. In the present study, previously defined future scenarios, in the form of land-use/land-cover grids, were examined relative to their impact on surface-water conditions (e.g., surface runoff and sediment yield). These hydrological outputs were estimated for the baseline year of 2000 and predicted twenty years in the future as a demonstration of how new geographic information system-based hydrologic modeling tools can be used to evaluate the spatial impacts of urban growth patterns on surface-water hydrology.     

Impact of automobile emissions on the levels of platinum and lead in Accra,Ghana

Examination of car fleet records in Accra demonstrates an increasing proportion of catalytic converter-equipped cars in the relatively old car fleet (average age 13 years) due to their import from developed countries. However, only leaded petrol is sold in Ghana. Lead anti-knocking additives, which are known to affect catalyst activity and promote thermal sintering and mechanical abrasion, may increase Pt emissions. This possible synergism prompted the concomitant determination of Pb and Pt levels in road dust and roadside soils in Ghana. Both metals followed traffic density with higher concentrations in urban areas compared to remote sites. In urban areas, the range for Pb (365 +/- 93 microg g(-1) for dust and 291 +/- 76 microg g(-1) for soil) reflects precatalyst levels in Europe and the US, while the range for Pt (39 +/- 24 ng g(-1) for dust and 15 +/- 5.3 ng g(-1) for soil) is typical for the same countries. The elevated Pt concentrations were unexpected due to recent introduction of catalysts to Ghana compared to the prolonged use of catalysts in Europe and the US.     

Atmospheric deposition of silver and thallium since 12 370 14C years BP recorded by a Swiss peat bog profile, and comparison with lead and cadmium

A peat core from an ombrotrophic bog in Switzerland provides the first complete, long-term record (14 500 years) of atmospheric Ag and Tl deposition. The lack of enrichment of Ag and Tl in the basal peat layer shows that mineral dissolution in the underlying sediments has not contributed measurably to the Ag and Tl inventories in the peat column, and that Ag and Tl were supplied exclusively by atmospheric deposition. The temporal and spatial distribution of modern peaks in Ag and Tl concentrations are similar to those of Pb which is known to be immobile in peat profiles. Silver and Tl, therefore, are effectively immobile in the peat bog also, allowing an atmospheric deposition chronology to be reconstructed. Silver concentrations vary by up to 114x and Tl up to 241x. While Holocene climate change and land use history can explain the variation in metal concentrations and enrichment factors (EF) in ancient peats (i.e. pre-dating the Roman Period), anthropogenic sources have to be invoked to explain the very high EF values (up to 123 in the case of Ag and 12 in the case of Tl) in peat samples since the middle of the 19th Century. The "natural background" EF of Tl in ancient peats is remarkably close to unity, indicating a lack of significant enrichment of this element in atmospheric aerosols due to chemical weathering of crustal rocks. Silver, on the other hand, shows a pronounced enrichment from 8030 to 5230 (14)C years BP (12x compared to crustal rocks); this may be due to weathering phenomena or biological processes, both of which are driven by climate. Even compared to the natural enrichment of Ag during the mid-Holocene, however, the enrichments of Ag and Tl in modern peats from the Industrial Period are at least an order of magnitude greater. The Pb/Ag and Tl/Ag ratios show that Pb and Tl are preferentially released, compared to Ag, during smelting of argentiferous Pb ores mined during the Roman and Medieval Periods.     

Attributes of reliable long-term landscape-scale studies: Malpractice insurance for landscape ecologists

Monitoring long-term change in forested landscapes is an intimidating challenge with considerable practical, methodological, and theoretical limitations. Current field approaches used to assess vegetation change at the plot-to-stand scales and nationwide forest monitoring programs may not be appropriate at landscape scales. We emphasize that few vegetation monitoring programs (and, thus, study design models) are designed to detect spatial and temporal trends at landscape scales. Based primarily on advice from many sources, and trial and error, we identify 14 attributes of a reliable long-term landscape monitoring program: malpractice insurance for landscape ecologists. The attributes are to: secure long-term funding and commitment; develop flexible goals; refine objectives; pay adequate attention to information management; take an experimental approach to sampling design; obtain peer-review and statistical review of research proposals and publications; avoid bias in selection of long-term plot locations; insure adequate spatial replication; insure adequate temporal replication; synthesize retrospective, experimental, and related studies; blend theoretical and empirical models with the means to validate both; obtain periodic research program evaluation; integrate and synthesize with larger and smaller scale research, inventory, and monitoring programs; and develop an extensive outreach program. Using these 14 attributes as a guide, we describe one approach to assess the potential effect of global change on the vegetation of the Front Range of the Colorado Rockies. This self-evaluation helps identify strengthes and weaknesses in our program, and may serve the same role for other landscape ecologists in other programs.     

Impact of desertification on temperature trends in the Middle East

The intense interest in desertification and climate change has stimulated detailed studies of temperature records in many areas of the world. In this investigation, the temperature records from the Middle East region are analyzed over the period 1950–1990. Results reveal a linear, statistically significant temperature increase of 0.07 °C/decade over the 41-year period. An analysis of spatial controls on these temperature changes reveals a warming effect associated with both overgrazing and the degree of human-induced desertification. The results of this study are consistent with theoretical and empirical studies predicting and demonstrating a warming signal associated with these land surface changes in the world's dryland areas.     

Establishing a standard Sonoran Reference Plant and its application in monitoring industrial and urban pollution throughout the Sonoran Desert

Using analyses from honey mesquite (Prosopis glandulosa) leaves from nearly pristine locations in Arizona, an inorganic plant concentration standard is proposed for use as a Sonoran Reference Plant (SRP). Such a standard can be used as a monitoring device for different anthropogenic pollution sources throughout the Sonoran Desert. To test the application of the SRP, honey mesquite leaves were collected at different sites in southern Arizona and their chemical fingerprints compared to SRP. Sources of element origin were identified through factor analysis and correlation matrices. A terrestrial factor was found in leaves from all sites. Anthropogenic factors varied for different sites. Mesquite leaves accumulated significant amounts of elements originating from copper smelters (As, Sb) and urban pollution (La, Sm, Ce, V). These pollutants are small-sized and have been linked to human lung diseases. Mesquite is a deciduous tree; the yearly comparison of mesquite leaf element concentration spectra to the SRP standard can be used to determine seasonal improvement or deterioration of environmental quality in a particular area.